Palladium‐Catalyzed Annulation of Acyl Fluorides with Norbornene via Decarbonylation and CO Reinsertion

Abstract

Ap alladium-catalyzed annulation of acyl fluorides with norbornene is described. This study reports the first example of an annulationo fa cyl fluorides in the presence of a transition-metal catalyst. Polycyclic ketones are obtained from the cleavage of the CÀFa nd CÀHb onds of the acyl fluoridea nd the rearrangement of the carbonyl moiety by decarbonylation and CO reinsertion. Scheme1.Transition-metal-catalyzed CÀCbondformation reactionsofa cyl fluorides.

Decarbonylative cycloaddition of 1H-indene-1,2,3-trione and norbornene via rhodium(i)-catalyzed carbon–carbon bond cleavage

“…6.8 mg (yield: 25%). 1 H NMR (400 MHz,chloroformd) d 7.77 (d,J = 8.0 Hz,1H),7.69 (d,J = 1.5 Hz,1H),2H),7.58 (dd,J = 7.9,1.6 Hz,1H),2H),1H),3.20 (d,J = 6.1 Hz,1H),2.63 (d,J = 4.0 Hz,1H),2.55 (d,J = 6.1 Hz,1H),2.47 (d,J = 4.1 Hz,1H),1.70 (ddddd,J = 23.2,15.9,12.0,8.2,4.1 Hz,2H), 1.52-1.35 (m, 2H), 0.98 (dt, J = 10.6, 1.5 Hz, 1H), 0.88 (dt, J = 10.6, 1.9 Hz, 1H); 13 C NMR (101 MHz, chloroform-d) d 208.47, 157.97, 148.02, 140.30, 137.98, 128.97, 128.34, 127.51, 126.89, 124.64, 123.57, 56.26, 48.13, 41.40, 40.46, 32.34, 28.93, 28.73;IR(KBr): n 3057, 3002, 2937, 1756, 1690, 1487, 1463, 1369, 1276 O: 275.1436O: 275. , found: 275.1437-one (3e 0 ) 21 White solid: mp 106-108 1C. 10.1 mg (yield: 37%).…”

Recent Advances in C–F Bond Activation of Acyl Fluorides Directed toward Catalytic Transformation by Transition Metals, N-Heterocyclic Carbenes, or Phosphines

“…When the Pd/P(dcpe) ratio is 1:2, decarbonylation is facilitated by the presence of a vacant coordination site on the metal center, and the stripped CO makes the intermediate more stable (Scheme 15(b)). 42 Optimization of the reaction system led to the development of Pd(OAc)2/PCy3 catalytic system, and a suitable reaction protocol for (hetero)aroyl and alkenylated acyl fluorides was established. In this transformation, the C-F bond of acyl fluorides is activated by palladium followed by the activation of the ortho C-H bond accompanied by the CO rearrangement during the reaction process, leading to the synthesis of a series of polycyclic ketones in good yields.…”

“…Subsequently, Ogiwara and Sakai developed the palladium-catalyzed intermolecular cyclization between acyl fluorides and norbornene derivatives (Scheme 16a). 42 Optimization of the reaction system led to the development of a Pd(OAc) 2 /PCy 3 catalytic system, and a suitable reaction protocol for (hetero)aroyl and alkenylated acyl fluorides was…”

Decarboxylative Cross-Coupling of Acyl Fluorides with Potassium Perfluorobenzoates

“…As organic electrophiles for cross-couplings, acyl fluorides can easily be prepared from the corresponding carboxylic acids . In recent years, acyl fluorides have attracted a great deal of attention due to their powerful capabilities in various decarbonylative cross-coupling reactions. , Furthermore, acyl fluorides have served as acyl sources under transition metal catalysis to generate various aldehydes , and ketones in a carbonyl-retentive manner. During the course of our continuing studies of the transition metal-catalyzed transformations of acyl fluorides, we have encountered unique reactivities of the C­(acyl)–F bond.…”

“…In particular, dimethylamino ( 3h ), cyano ( 3j ), ketone ( 3k ), and ester ( 3l ) substituents were well tolerated. To our delight, p -nitrobenzoyl fluoride, which is less mentioned in previous work, − could be transformed to the desired product 3m in 76% yield. In addition, halogenated acyl fluorides, especially o -iodobenzoyl fluoride, could also be applied to this reaction, affording ketones 3n–3q in 85–96% yields.…”